Preparation process and purification process of cyclic ester
A process for preparing a cyclic ester by reacting an .alpha.-hydroxycarboxylic acid or an .alpha.-hydroxycarboxyliclic acid ester with an orthoester. A process for purifying a cyclic ester by containing water and acid as impurities by adding an orthoester to a cyclic ester obtained by reaction of a reaction mixture including an .alpha.-hydrocarboxylic acid or an .alpha.-hydroxycarboxyliclic acid ester. According to the present invention, a high-purity cyclic ester containing small amounts of impurities such as water and an acid component can be provided.
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Claims
1. A process to prepare a cyclic ester product comprising heating a reaction mixture comprising an.alpha.-hydroxycarboxyliclic acid or an.alpha.-hydroxycarboxylic acid ester represented by the formula R.sup.1 R.sup.2 C (OH) COOR.sup.3, wherein R.sup.1, R.sup.2 and R.sup.3 are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or a mixture of said.alpha.-hydroxycarboxylic acid and said.alpha.-hydroxycarboxylic acid ester as a raw material, wherein at least one orthoester is added to the raw material before the heating, or to the reaction mixture during the heating or after completion of the heating, said at least one orthoester being represented by the formula (I)
2. The process according to claim 1 wherein an acid and water are present in at least one of the raw material, the reaction mixture or the cyclic ester product, and are converted into an alcohol and an ester with the orthoester, and the thus formed alcohol and ester are then removed.
3. The process according to claim 2 wherein the formed alcohol and ester are removed by distillation.
4. The process according to claim 1 wherein the orthoester is a compound selected from the group consisting of methyl orthoformate, ethyl orthoformate, methyl orthoacetate and ethyl orthoacetate.
5. The process according to claim 1 wherein the.alpha.-hydroxycarboxyliclic acid or the.alpha.-hydroxycarboxyliclic acid ester as the raw material is lactic acid or a lactic acid ester, and the cyclic ester is a lactide.
6. The process according to claim 5 wherein the lactic acid ester is obtained by (A) producing lactonitrile from prussic acid and acetaldehyde, (B) hydrating lactonitrile obtained by the previous step (A) to form lactamide, (C) forming the lactic acid ester and formamide from lactamide obtained by the previous step (B) and a formic acid ester of the formula HCOOR, wherein R is an alkyl group having 1 to 6 carbons, and (D) separating formamide from the products obtained in the previous step (C), dehydrating the formamide to form prussic acid, and recycling the formed prussic acid.
7. The process according to claim 5 wherein the lactic acid ester is methyl lactate, and the cyclic ester is a lactide.
8. The process according to claim 1 wherein the.alpha.-hydroxycarboxyliclic acid or the.alpha.-hydroxycarboxyliclic acid ester as the raw material is a.alpha.-hydroxyisobutylic acid or methyl.alpha.-hydroxyisobutylate, and the cyclic ester is tetramethyl glycolide.
9. A process to purify a cyclic ester product containing a cyclic ester, and water and an acid asL( impurities, which comprises adding at least one orthoester represented by the formula (I)
10. The process according to claim 1 wherein the.alpha.-hydrocarboxylic acid is selected from the group consisting of glycolic acid, lactic acid and.alpha.-hydroxyisobutylic acid; and the.alpha.-hydroxycarboxyliclic acid ester is selected from the group consisting of methyl glycolate, ethyl glycolate, methyl lactate, ethyl lactate, butyl lactate, methyl.alpha.-hydroxyisobutylateand ethyl.alpha.-hydroxyisobutylate.
11. The process according to claim 10 wherein the orthoester is selected from the group consisting of methyl orthoformate, ethyl orthoformate, propyl orthoformate, methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate, methyl orthopropionate, ethyl orthopropionate, methyl orthoisopropionate, ethyl orthoisopropionate, methyl orthobutylate, ethyl orthobutylate, methyl orthoisobutylate and ethyl orthoisobutylate.
12. The process according to claim 1 wherein the orthoester is in an amount of 0.5 to 10 equivalents of a total value of an acid value and a water content of the raw material, as defined by the following equation: total value=acid value in meq/kg+water content in (ppm/18).
13. The process according to claim 12 wherein the orthoester is in an amount of 1 to 5 equivalents of the total value.
14. The process according to claim 13 wherein the process is carried out at a temperature of 25 to 300.degree. C.
15. The process according to claim 14 wherein the temperature is 50 to 250.degree. C.
16. The process according to claim 14 wherein the temperature is 100 to 200.degree. C.
17. The process according to claim 16 wherein the heating is carried out for a time of 0.1 to 10 hours.
18. The process according to claim 17 wherein the time is 0.2 to 5 hours.
19. The process according to claim 17 wherein the time is 0.5 to 2 hours.
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Type: Grant
Filed: Sep 22, 1997
Date of Patent: May 4, 1999
Assignee: Mitsubishi Gas Chemical Co., Inc. (Tokyo)
Inventors: Hideharu Kurashima (Kanagawa-ken), Yasushi Higuchi (Kanagawa-ken), Masahiro Kurokawa (Kanagawa-ken)
Primary Examiner: Laura L. Stockton
Law Firm: Frishauf, Holtz, Goodman, Langer & Chick, P.C.
Application Number: 8/934,638
International Classification: C07D31906; C07D31912;
